Alkoxy metal salts of succinamic acids



United States Patent C 3 Claims. (Cl. 260-429) ABSTRACT OF THEDISCLOSURE Metal salts of succinamic acids are provided which areeffective for inhibiting petroleum distillate fuel oils againstsedimentation, screen clogging, emulsification and rusting of ferrousmetal surfaces in contact therewith. These metal salts have thefollowing formula:

wherein R is a monovalent aliphatic hydrocarbon group having between 4and 30 carbon atoms and a tertiary carbon atom linked to the nitrogenatom; R is a saturated aliphatic hydrocarbon group; M is a divalentmetal; and n is an integer of O to 10.

This invention is a division of our copend-ing application Ser. No.208,127, filed July 6, 1962, now Patent No. 3,264,075, issued Aug. 2,1966, and relates to the improvement of non-lubricating petroleumfractions. It is more particularly concerned with distillate fuel oilscontaining additives adapted to inhibit the appearance of sedimentduring prolonged storage periods, to prevent screenclogging, preventrusting of ferrous metal surfaces, and to inhibit the fuel oils againstemulsification.

It is well known that fuel oils are prone to form sludge or sedimentduring periods of prolonged storage. This sediment, of course, has anadverse effect on burner operation, because it has a tendency to clogscreens and nozzles. In addition to sediment formed during storage, mostfuel oils contain other impurities, such as rust, dirt, and entrainedwater. The sediment and impurities tend to settle out on equipmentparts, such as nozzles, screens, filters, etc., thereby clogging themand causing the equip ment to fail.

A further factor, incident to the storage and handling of fuel oils, isthe breathing of storage vessels. This results in the accumulation ofconsiderable amounts of water in the tanks, which presents a problem ofrusting in the tanks. Then, when the oil is removed for transportation,sufficient water may be carried along to cause rusting of ferrous metalsurfaces in pipelines, tankers, and the like.

Generally, it has been the practice to overcome the aforedescri-beddifiiculties with a separate additive for each purpose, i.e., with asediment inhibitor, an antiscreen clogging agent, and an antirust agent.The use of several additives, however, gives rise to problems ofadditive compata-bility, thus restricting the choice of additivecombinations. In addition, of course, the use of a plurality ofadditives unduly increases the cost of the fuel.

It has now been found that all three problems, i.e., sedimentation,screen clogging, and rusting, can be solved by the use of a single fueloil addition agent. It has been discovered that a distillate fuel oilcontaining minor amounts of certain metal salts of certain amic acidsare effectively inhibited, simultaneously, against all threeaforementioned difiiculties and of considerable importance, withoutinducing objectionable emulsification characteristics to the distillatefuel oils.

Accordingly, it is a broad object of this invention to provide a fueloil having properties improved with a minimum number of addition agents.Another object is to provide a fuel oil having a single additive adaptedto inhibit sedimentation, to prevent screen clogging, and to preventrusting of ferrous metal surfaces with which it comes in contact. Aspecific object is to provide a fuel oil containing certain metal saltsof amic acids that achieves these results. Other objects and advantagesof this invention will become apparent to those skilled in the art fromthe following detailed description.

The present invention provides a distillate fuel oil containing a minoramount, suflicient to inhibit sedimentation and screen clogging, and toprevent rusting of ferrous metal surfaces in contact therewith withoutinducing objectionable emulsification characteristics to said fuel oil,of a compound selected from the group consisting of (l) a metal salt ofa succinamic acid having the formula- I (BET-(EH2 o 000 -M RHN o nwherein R is a monovalent aliphatic hydrocarbon radical having betweenabout 4 and about 30 carbon atoms and a tertiary carbon atom linked tothe nitrogen atom; M is a metal selected from the group consisting ofdivalent copper, and metals from Groups II-A, II-B, III-A, IV-A, andVIII of the Periodic Chart of the Elements and n is a small whole numberequal to the valence of M; (2) an alkoxy metal salt of succinamic acidhaving the formulawherein R, R and M and n is an integer of 1 andpreferably 1 to 6.

The addition agents utilizable in the fuel oil compositions of thisinvention are metal salts of amic acids that have the formula:

have the aforesaid significance, to 5, or more, such as 1 to 10,

o COOH RHN o wherein R is an aliphatic hydrocarbon radical of analiphatic, primary tertiary alkyl amine containing between about 4 andabout 30 carbon atoms and a tertiary carbon atom attached to thenitrogen atom. The amic acids contemplated herein can be made by anymethod for preparing such compounds that is known to the art. They areproduced, preferably, by Warming succinic acid anhydride with a primarytertiary-alkyl amine having between about 4 and about 30 carbon atomsper molecule to form the monoamide of the acid. This can be done readilyby heating the mixture of anhydride and amine at a temperature of l50 C.for a period of time varying between one and 3 hours. The additionoccurs readily without the formation of water. Less desirably, the amicacids can be prepared by the controlled reaction between succinic acidand the amine, with the elimination of one mole of water per mole ofamic acid produced. Care must be exercised to avoid the eliminatiOn oftwo moles of water to form the cyclic imide.

The amines that can be utilized to form the amic acids are the tertiaryalkyl, primary, monoamines in which a primary amino (-NH group isattached to a tertiary carbon atom; and mixtures thereof. These aminesall contain the terminal group,

CH3 Non-limiting examples of the amine reactants are t-butyl primaryamine, t-hexyl primary amine, t-octyl primary amine, t-decyl primaryamine, t-dodecyl primary, amine, t-tetradecyl primary amine, t-octadecylprimary amine, teicosyl primary amine, t-tetracosyl primary amine, andt-triacontyl primary amine. The amine reactants can be prepared inseveral ways well known to those skilled in the art. Specific methods ofpreparing the t-alkyl primary amines are disclosed in the Journal ofOrganic Chemistry, vol. 20, p. 295 at seq. (i955). Mixtures of suchamines can be made from a polyolefin fraction (e.g., polypropylene andpolybutylene cuts) by first hydrating with sulfuric acid and water tothe corresponding alcohol, converting the alcohol to alkyl chloride withammonia, under pressure, to produce the t-alkyl primary amine mixture.

The salts of the succinamic acids contemplated herein are metal saltswherein the salt-forming metal is an appropriate metal from Groups IB,Ii-A, iii-B, HLA, IVA and VIII of the Periodic Chart of the Elements, asset forth in Introductory College Chemistry" by H. G. Deming (John Wileyand Sons). Preferred salt-forming metals are cupric Cu, Ba, Ca, Sr, Mg,Zn, Cd, Al, Pb and Fe. The method of forming the metal salts of thisinvention is not a critical factor herein. Thus, any of the usualmethods known to those skilled in the art can be utilized. Typicalmethods for forming the normal salt (Formula I) include forming analkali-metal salt (e.g., by neutralizing with caustic), and then using adouble decomposition reaction with a salt of the desired metal (e.g.,CuSo neutralizing the acid with a metal alcoholate (e.g., bariummethylate); and heating with an oxide of the metal (e.g., magnesiumoxide). Suitably, the non-polar solvents can be used in the salt-formingoperation. In many cases, the metal salts of this invention can be usedin solution in the solvent, for greater ease of handling. Thus,concentrates of the salts of this invention in amounts varying betweenand about 90%, by weight, in a solvent are contemplated. Suchconcentrates are then added to the fuel oil to give the desired finalconcentration in the fuel. Suitable solvents are benzene, toluene,xylene, light lubricating oil, Sovasol #5 and kerosene. The alkoxy metalsalts (Formula II) can be prepared by heating one mole of the succinamicacid with one mole of an appropriate M(O-alkyl) compound (e.g.,magnesium methylate); and the complex alkoxy metal salts (Formula Hi)can be prepared by heating the succinamic acid with two or more moles ofthe stated M(O- alkyl) compound.

The fuel oils that are improved in accordance with this invention arehydrocarbon fractions having an initial boiling point of at least about100 F. and an end boiling point no higher than about 750 F., and boilingsubstantially continuously throughout their distillation range. Suchfuel oils are generally known as distillate fuel oils. It is to beunderstood, however, that this term is not restricted to straight-rundistillate fractions. The distillate fuel oils can be straight-rundistillate fuel oils, cata lytically or thermally cracked (includinghydrocracked) distillate fuel oils, or mixtures of straight-rundistillate fuel oils, naphthas and the like with cracked distillatestocks. Moreover, such fuel oils can be treated in accordance with wellknown commercial methods, such as, acid or caustic treatment,hydrogenation, solvent refining, clay treatment, etc.

The distillate fuel oils are characterized by their relatively lowviscosities, pour points, and the like. The principal property whichcharacterizes the contemplated hydrocarbons, however, is thedistillation range. As mentioned hereinbefore, this range will liebetween about 100 F. and about 750 F. Obviously, the distillation rangeof each individual fuel oil will cover a narower boiling range falling,nevertheless, within the above-specified limits. Likewise, each fuel oilwill boil substantially continuously throughout its distillation range.

Particularly contemplated among the fuel oils are Nos. 1, 2, and 3 fueloils used as heating and diesel fuel oils, and jet combustion fuels. Thedomestic fuel oils generally conform to the specifications set forth inASTM Specifications D39648T. Specifications for Diesel fuels are definedin ASTM Specifications D975-48T. Typical jet fuels are defined inMilitary Specification MIL-F-5624B.

The amount of the metal salt of succinamic acid that is added to thedistillate fuel oil in accordance with this invention will depend uponthe intended purpose and the particular amic acid salt selected, as theyare not all equivalent in their activities. Some may have to be used tobe used in greater concentrations than others to be effective. In mostcases, in which it is desired to obtain all three beneficial results,namely, to inhibit sedimentation, to reduce screen clogging, and toprevent rusting of ferrous metal surfaces, additive concentrationsvarying between 10 pounds per thousand barrels of oil and about 200pounds per thousand barrels of oil will be employed. It may not alwaysbe desired, however, to accomplish all three aforementioned results. Insuch cases, where it is desired to elfect only one or two results, lowerconcentrations can be used. Thus, if it is desired only to prevent rustunder dynamic conditions, as in a pipeline, it has been found thatconcentrations as low as about 5 p.p.m., i.e., about one pound ofadditive per thousand barrels of oil, are effective. In general,therefore, the amount of metal salt of amic acid that can be added tothe distillate fuel oil, in order to achieve a beneficial result, willvary generally between about one pound per thousand barrels of oil andabout 200 pounds per thousand barrels of oil. Preferably, it will varybetween about 10 and about 200 pounds per thousand barrels of oil.

If it is desired, the fuel oil compositions can contain other additivesfor the purpose of achieving other results. Thus, for example, there canbe present foam inhibitors and ignition and burning quality improvers.Examples of such additives are silicones, dinitropropane, amyl nitrate,metal sulfonates, and the like.

The following specific examples are for the purpose of illustrating thefuel oil compositions of this invention, and of exemplifying thespecific nature thereof. It is to be strictly understood, however, thatthis invention is not to be limited by the particular additives and fueloils, or to the operations and manipulations described therein. Otheramic acid salts and fuel oils, as discussed hereinbefore, can be used,as those skilled in the art will readily appreciate.

The amine reactants used in the specific working examples are mixturesof pure amines. Amine A is a mixture of primary amines having a carbonatom of a tertiary butyl group attached to the amino (-NH group andcontaining 12 to 15 carbon atoms per amine molecule and averaging 12carbon atoms per molecule. This mixture contains, by weight, aboutpercent tertiarydodecyl primary amine, about 10 percenttertiary-pentadecyl primary amine, and relatively small amounts, i.e.,less than about 5 percent of amines having less than 12 or more than 15carbon atoms. Amine B is a mixture of tertiary-alkyl primary aminescontaining 18 to 24 carbon atoms per molecule and averaging about 20*carbon atoms per molecule. It has a tertiary carbon atom attached to theNH group and contains, by weight, about 40 percent tertiary-octadecylprimary amine, about 30 percent tertiary-eicosyl primary amine, about 15percent tertiary-docosyl primary amine, about 10 percenttertiary-tetracosyl primary amine, and a small amount, less thanpercent, other amines as high as tertiary-triacontyl primary amine.

In the following examples, solvents were used to facilitate handling theproducts. Among the solvents used herein are Sovasol #5 and a lightlubricating oil. Sovasol #5 is an aliphatic petroleum solvent having aboiling range of 320-381 R, an API Gravity of 45.5 and an Aniline Pointof 112 F. The light lubricating oil" is a solvent-refined paraffinic oilhaving an API Gravity of 33, a pour point of 20 F., a viscosity of 128seconds Saybolt at 100 F., and a Viscosity Index of 105.

Example 1 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 100gms. (0.5 mole) of Amine A and 300 gms. of Sovasol #5 as a diluent wasstirred at 85l00 C. for approximately 2 hours to form the Amine Asuccinamic acid. To the above Amine A succinamic acid was added at roomtemperature with stirring 69 gms. (0.25 mole+6 gms. excess) of CuSO .5HO previously dissolved in 100cc. of water and then 21 gms. (0.5 tmole+1gm. excess) of NaOH previously dissolved in 100 cc. of water. Themixture was stirred at 100 C. for 6 hours. The reaction product wasseparated from the water layer and filtered by gravity. The finalproduct, the copper salt of the Amine A succinamic acid, which contained66% Sovasol #5 was fluid at room temperature.

Analysis.-Cu, 1.72%; N, 1.32%.

Example 2 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 100gms. (0.5 mole) of Amine A and 100 cc. of benzene as a diluent wasstirred at 85 C. for 2 hours to form the Amine A succinamic acid. TheAmine A succinamic acid was then added at room temperature with stirringto 6 gms. (0.25 mole) of Mg in the form of a Mg methylate solution. Themixture was gradually heated to 150 C. to distill out the methanol. Thereaction product, the Mg salt of Amine A succinamic acid, being viscous,was diluted with 312 gms. of xylene and filtered through filteringclays. The final product which contained 66 /s% xylene was clear andfluid at room temperature.

Analysis.-Estimated: Mg, 1.28%; N, 1.50%. Found: Mg, 1.28; N, 1.59.

Example 3 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 100gms. (0.5 mole) of Amine A and 150 cc. of xylene as a diluent wasstirred at 95 C. for 2 hours to form the Amine A succinamic acid. To theabove Amine A succinamic acid was added at room temperature withstirring 286 gms. of 12% Ba methylate solution (equivalent to 0.25 moleof Ba). The mixture was gradually heated to 175 C. to distill out thesolvent. The reaction product, the Ba salt of Amine A succinamic acid,being viscous, was diluted with 736 gms. of xylene and filtered throughfiltering clay. The final product which contained approximately 80%xylene was clear and fluid at room temperature.

Analysis.-Estimated: Ba, 3.2%; N, 0.7%. Found: Ba, 2.98%; N, 0.72%.

Example 4 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 100gms. (0.5 mole) of Amine A and 200 cc. of toluene was stirred at 85 C.for 2 hours to form the Amine A succinamic acid. To the above Amine Asuccinamic acid was added at room temperature with stirring 20 gms. (0.5mole) of NaOH dissolved in 200 cc. of methanol. The mixture wasgradually heated to 175 C. to form the sodium salt of Amine A succinamicacid. To the sodium salt of Amine A succinamic acid was then added atroom temperature 33 gms. (0.25 molef+5 gms. excess) of CaCl previouslydissolved in 200 cc. of methanol. The mixture was gradually heated to175 C. to form the Ca salt. The reaction product being viscous, wasdiluted with 200 cc. of benzene, filtered through filtering clay andtopped to 175 C. under house vacuum. The final product, the Ca salt ofAmine A succinamic acid, weighed 150 gms. and was diluted with 150 gms.of xylene.

Analysis.Estimated: Ca, 3.15% N, 2.2%. Found: Ca, 3.23%; N, 2.28%.

Example 5 A mixture of 50 gms. (0.5 mole) of succinic anhy' dride, 100gms. (0.5 mole) of Amine A and 150 cc. of xylene was stirred at C. for 2hours to form the Amine A succinamic acid. To the above Amine Asuccinamic acid was added at room temperature with stirring 20 gms. (0.5mole) of NaOH dissolved in 200 cc. of methanol. The mixture wasgradually heated to 175 C. to form a sodium salt of the Amine Asuccinamic acid. To the sodium salt of Amine A succinamic acid was thenadded at room temperature 44 gms. (0.25 mole+10 gms. excess) of ZnCldissolved in 200 cc. of methanol. The mixture was gradually heated to175 C. to form a Zn salt of the Amine A succinamic acid. The reactionproduct was diluted with 500 cc. of benzene, filtered through filteringclay and topped to C. under house vacuum to remove the benzene. Thefinal product, the Zn salt of the Amine A succinamic acid, which weighed156 gms. was viscous and diluted with 156 gms. of xylene.

Analysis-Estimated: Zn, 5.02%; N, 2.10%. Found: Zn, 5.05%; N, 1.90%.

Example 6 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 100gms. (0.5 mole) of Amine A and 100 cc. of toluene was stirred at 95 C.for 2 hours to form the Amine A succinamic acid. To the above Amine Asuccinamic acid was added at room temperature with stirring 11.5 gms.(0.5 mole) of sodium in the form of a sodium methylate solution. Themixture was gradually heated to C. and was held at 150 C. for 2 hours toinsure the complete formation of the sodium salt of the Amine Asuccinamic acid. To the sodium salt of the Amine A succinamic acid wasthen added at room temperature with stirring 30 gms. /6 mole+3 gms.excess) of ferric chloride dissolved in 200 cc. of methanol. The mixturewas gradually heated to 150 C. and was held at 150 C. for 3 hours. Thereaction product was diluted with 200 cc. of benzene, filtered throughfiltering clay and topped to 60 C. under a pressure of 3 mm. of mercury.The final product, the iron salt of Amine A succinamic acid, whichweighed 147 gms. was viscous at room temperature and diluted with 147gms.-of xylene.

Analysis.-Estimated: Fe, 2.9%; 2.2%. Found: Fe, 3.42%; 2.25%.

Example 7 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 100gms. (0.5 mole) of Amine A and 150 cc. of xylene was stirred at 95 C.for 2 hours to form the Amine A succinamic acid. To the above Amine Asuccinamic acid was added at room temperature with stir ring 4.5 gms. ,6mole) of aluminum in the form of an aluminum butylate solution. Themixture was gradually heated to C. to form the aluminum salt of theAmine A succinamic acid. The reaction product was diluted with 500 cc.of benzene, filtered through filtering clay and topped to 150 C. underthe house vacuum. The

7 final product which weighed 130 gms. was viscous and diluted with 130gms. of xylene.

Armlysis.-Estimated: Al, 1.4%; N, 2.3%. Found: Al, 1.25%; N, 2.37%.

Example 8 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 150gms. (0.5 mole) of Amine B and 150 cc. of xylene was stirred at 95 C.for 4 hours to form the Amine B succinamic acid. To the above Amine Bsuccinamic acid was added at room temperature with stirring 6 gms. (0.25mole) of Mg in the form of a Mg methylate solution. The mixture wasgradually heated to 175 C. to form the Mg salt of Amine B succinamicacid. The reaction product being viscous, was diluted with 206 gms. oflight lubricating oil and filtered through filtering clay.

Anal sis.Estimated: Mg, 1.34%; N, 1.7%. Found: Mg, 1.49%; N, 1.87%.

Example 9 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 150gms. (0.5 mole) of Amine B and 150 cc. of xylene was stirred at 95 C.for 2 hours to form the Amine B succinamic acid. To the above Amine Bsuccinamic acid was added at room temperature with stirring 20 gms. (0.5mole) NaOH previously dissolved in 200 cc. of methanol. The mixture wasgradually heated to 175 C. to form the sodium salt of the Amine Bsuccinamic acid. To the Na salt of the Amine B succinamic acid was thenadded 420 gms. of light lubricating oil and 33 gms. (0.25 mole+ gms.excess) of CaCl previously dissolved in 200 cc. of methanol. The mixturewas gradually heated to 175 C. and was held there for 3 hours to insurethe complete formation of the Ca salt. The reaction product was filteredthrough filtering clay. The final product, the calcium salt of the AmineB succinamic acid, which contains 66 /s% light lubricating oil was fluidat room temperature.

Analysis.Estimated: Ca, 1.85%; N, 1.32%. Found: Ca, 1.57%; N, 1.12%.

Example 10 A mixture of 50 gms. (0.5 mole) of succinic anhydride. 150gms. (0.5 mole) of Amine B and 150 cc. of toluene was stirred at 95 C.for 2 hours to form the Amine B succinamic acid. To the above Amine Bsuccinamic acid was added at 50 C. with stirring 286 gms. of 12% Bamethylate solution (0.25 mole of Ba). The mixture was gradually heatedto 175 C. The reaction product being viscous, was diluted with 468 gms.of light lubricating oil and filtered through filtering clay. The finalproduct, the Ba salt of the Amine B succinamic acid, which contained 66/3 light lubricating oil, was fluid at room temperature.

Analysis.Estimated: Ba, 4.8%; N, 0.9%. Found: Ba, 2.33%; N, 0.86%.

Example 11 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 150gms. (0.5 mole) of Amine B and 150 cc. of xylene was stirred at 95 C.for 2 hours to form the Amine B succinamic acid. To the above Amine Bsuccinamic acid was added at room temperature with stirring gms. (0.5mole) of NaOH previously dissolved in 250 cc. of methanol. The mixturewas gradually heated to 175 C. to form the Na salt of the Amine Bsuccinamic acid. To the Na salt of the Amine B succinamic acid was thenadded at room temperature with stirring 432 gms. of light lubricatingoil and 44 gms. (0.25 mole-l-lO gms. excess) of ZnCl previouslydissolved in 250 cc. of methanol. The mixture was gradually heated to175 C. and was held at 175 C. for 3 hours to insure the completeformation of the Zn salt of the Amine B succinamic acid. The product wasfiltered through filtering clay. The final product which contained 66/3% light lubricating oil was fluid at room temperature.

Analysis.Estimated2 Zn, 2.5%; N, 1.08%. Found: Zn, 2.91%; N, 1.08%.

Example 12 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 150gms. (0.5 mole) of Amine B, 206 gms. of light lubricating oil and 100cc. of benzene was stirred at C. for 2 hours to form the Amine Bsuccinamic acid. To the above Amine B succinamic acid was added at roomtemperature with stirring 10.08 gms. (0.25 mole) of MgO previously mixedwith 20 cc. of water to form a paste. The mixture was gradually heatedto 175 C. and was held at 175 C. for 2 hours. The reaction product wasthen filtered through filtering clay. The final product, the Mg salt ofthe Amine B succinamic acid, which contained 50% light lubricating oilwas fluid at room temperature.

Analysis.-Estimated: Mg, 1.4%; N, 1.7%. Found: Mg, 1.24%; N, 1.58%.

Example 13 A mixture of 50 gms. (0.5 mole) of succinic anhydride, gms.(0.5 mole) of Amine B, 206 gms. of light lubri eating oil and 100 cc. ofbenzene was stirred at 100 C. for 2 hours to form the Amine B succinamicacid. To the above Amine B succinamic acid was added at room temperaturewith stirring 14.6 gms. (0.25 mole) of Mg(OH) The mixture was graduallyheated to C. and was held at 175 C. for 30 minutes. The product Was thenfiltered through filtering clay. The final product, the Mg salt of AmineB succinamic acid, which contained 50% light luibricating oil was fluidat room temperature.

Analysis.Estimated: Mg, 1.4%; N, 1.7%. Found: Mg, 1.28%; N, 1.52%.

Example 14 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 150gms. (0.5 mole) of Amine B and 250 cc. of xylene was stirred at 95 C.for 2 hours to form the Amine B succinamic acid. The Amine B succinamicacid was then added at room temperature with stirring to 11.5 gms. (0.5mole) of Na in the form of a Na methylate solution. The mixture wasgradually heated to 150 C. and was held at 150 C. for 2 hours to insurethe complete formation of the Na salt of Amine B succinamic acid. The Nasalt, diluted with 750 cc. of benzene, was then added at roomtemperature with stirring to 76.5 gms. (0.25 mole+7 gms. excess) of PbCldissolved in 2500 cc. of distilled water. The mixture was stirred at 100C. for 8 hours to insure the complete formation of the lead salt. Thelead salt was separated from the water layer, filtered through Hyfloclay and topped to 150 C. under house vacuum. The final product, thelead salt of Amine B succinamic acid, which weighed 228 gms., theory 252gms. was viscous at room temperature and diluted with 228 gms. ofxylene.

Analysis.-Estimated: Pb, 10.0%; N, 1.3%. Found: Pb, 9.7%; N, 1.53%.

Example 15 A mixture of 150 gms. (0.5 mole) of Amine A succinamic acid,diluted with 150 gms. of Solvesso #150, and 12 gms. (0.5 mole) of Mg inthe form of a Mg methylate solution was gradually heated to 150 C. toremove the methanol. The reaction product, being viscous, was dilutedwith 150 gms. of toluene and filtered through Hyfio clay. The finalproduct, the methoxy Mg salt of Amine A succinamic acid, which contained66 /3% solvent was clear and fluid at room temperature.

Analysis.Estimated: Mg, 2.6%. Found: Mg, 2.8%.

Example 16 A mixture of 50 gms. (0.5 mole) of succinic anhydride and 150gms. (0.5 mole) of Amine B was heated with stirring at 100-405 C. for 1/2 hours to form the Amine B succinamic acid. The Amine B succinamicacid, diluted with 600 gms. of Solvesso #150, was added at roomtemperature with stirring to 24.32 gms. (1 mole) of Mg in the form of 21Mg methylate solution. The mixture was gradually heated with stirring.At 82 C. the reaction mixture started to thicken but became fluid aftera quantity of 15 cc. of water was added. The reaction mixture was thenheated to 130 C. to remove the methanol. The final product, the complexmethoxy Mg salt of Amine -B succinamic acid, which contained 4equivalents of Mg and 73% Solvesso #150 was clear and fluid at roomtemperature.

Analysis.Estimated: Mg, 2.9%. Found: Mg, 2.81%.

Example 1 7 A mixture of 150 gms. (0.5 mole) of Amine A succinami-cacid, diluted with 450 gms. of Solvesso #150, and 24.32 gms. ('1 mole)of Mg in the form of a Mg methylate solution was gradually heated to 120C. to remove the methanol. The final product, the complex methoxy Mgsalt of Amine A succinamic acid, which contained 4 Mg equivalents and72% Solvesso #150 was clear and fluid at room temperature.

Analysis.Estimated: Mg, 3.8%. Found: Mg, 3.38%.

Example 18 A mixture of 50 gms. (0.5 mole) of succinic anhydride, 150gms. (0.5 mole) of Amine B and 600 gms. o'f Sl vesso #150 as a diluentwas heated with stirring at 95- 105 C. for 2 hours to form the Amine Bsuccinamic acid. The Amine B succinamic acid was then added at roomtemperature with stirring to 36.5 gms. (1.5 mole) of Mg in the form of21 Mg methyl'ate solution. The mixture was gradually heated withstirring. At 80 C. the the mixture started to thicken but became fluidafter a quantity of cc. of water had been added. The reaction mixturewas then gradually heated to 130 C. to remove the methanol. The finalproduct, the complex methoxy Mg salt of Amine B succinamic acid whichcontained 6 Mg equivalents and 72% Solvesso #150 was clear and fluid atroom temperature.

Analysis.-Es-timated: Mg, 4.3%. Found: Mg, 4.02%.

Example 19 A mixture of 150 gms. (0.5 mole) of Amine A succinamic acid,diluted with 450 gms. of Solvesso #150, and 36:48 gms. (1.5 moles) ofmagnesium in the form of a Mg methylate solution was gradually heatedwith stirring. At 82 C. before thickening occurred, a quantity of 20 cc.of water was added dropwise to the mixture. The mixture was thengradually heated to 125 C. to remove the methanol. The final product,the complex methoxy Mg salt of Amine A succinamic acid, which containedsix Mg equivalents and 72% Solvesso #150 was clear and fluid at roomtemperature.

Analysis.Estimated: Mg, 5.7%. Found: Mg, 5.42%.

SEDIMENTATION The test used to determine the sedimentationcharacteristics of the fuel oils is the 100 F. Stonage Test. In thistest, a 500-milliliter sample of the fuel oil under test is placed in aconvected oven maintained at 110 F. f r a period of 12 weeks. Then, thesample is removed from the oven and cooled. The cooled sample isfiltered through a tared asbestos filter (Gooch crucible) to removeinsoluble matter. The weight of such matter in milligrams is reported asthe amount of sediment. A sample of the blank, uninhibited oil is runalong with a fuel oil blend under test. The effectiveness of a fuel oilcontaining an inhibitor is determined by comparing the weight ofsediment formed in the inhibited oil with that formed in the uninhibitedoil.

Example 20 Additives described in the foregoing examples were blended intest fuel oils and the blends were subjected to the 110 F. Storage Test.The test results comparing 10 the blended fuels and uninhibited fuelsare set :forth in Table I. The test fuel oil is a blend of percentdistillate stock obtained from continuous catalytic cracking and 40percent straight-nun distillate stock. It has a boiling range of betweenabout 320 F. and about 640 F. and is a typical No. 2 fuel oil.

TABLE I.FUEL OIL STORAGE TEST, TWELVE WEEKS STORAGE AT 100 F.

Inhibitor Ooncn, 1b./ Sediment,

1,000 bbls. nag/liter Uninhibited fuel blend O 104 Uninhibited fuelblend-l-Ex. 2.. 50 2G Uninhibited fuel blend 0 100 Uninhibited fuelblend+Ex. 3.. 50 18 Uniuhibited fuel blend 0 104 Uninhibited fuelblend+Ex. 50 24 Uuinhibitod fuel blend 0 100 Uuinhibited fuel blend-l-Ex9 50 94 Uninhibited fuel blend..... 0 100 Uuinhibited fuel blend-l-Ex.50 41 Uninhibited fuel blend 0 25 Uninhibited fuel blend+Ex. 10 18Uninhibited fuel blend 0 Uninhibited fuel blend+Ex. 12.. 5O 24Uninhibited fuel blend 0 79 Uninhibiterl fuel blend+Ex. 50 35Uninhibited fuel blend.. 0 10 Uninhibited fuel blend+Ex. 25 5Uninhibited fuel blend... O 79 Uninhibited fuel blend+Ex. 50 2Uninhibited fuel blend 0 46 Uninhibited fuel blend+Ex. 18.. 10 9Uuinhibited fuel blend 0 46 Uninhibited fuel blend-l-Ex. l9 25 6 SCREENCLOGGING The anti-screen clogging characteristics of a fuel 01 weredetermined as vfollows: The test is conducted using a Sunstrand V3 or 81home fuel oil burner pump with a self-contained -mesh monel metalscreen. About 0.05 percent, by weight, of naturally-formed fuel oilsediment, composed of fuel oil, water, dirt, rust, and onganic sludge ismixed with 10 liters of the fuel oil. This mixture is circulated by thepump through the screen for 6 hours. Then, the sludge deposit on thescreen is washed off with normal pentane and filtered through a flaredGooch crucible. After drying, the material in Gooch crucible is washedwith a 5050 (volume) acetonemethanol mixture. The total organic sedimentis obtained by evaporating the pentane and the iacetonewmethanolfiltrates. Drying and weighing the Gooch crucile yields the amount ofinorganic sediment. The sum of the organic and inorganic deposits on thescreen can be reported in milligrams recovered or converted into percentscreen clogging.

Example 21 TABLE II.SCREEN CLOGGING TESTS Concn, Screen Inhibitorlb/1,000 Clogging,

bbls. Percent Uninhibited fuel blend 0 100 Uni :hibited fuel blend+Ex. 125 9 Uninliibited fuel blend+Ex. 2 25 27 Uninhibited fuel blend+Ex. 3 507 Uninhibited fuel blend+Ex. 4 10 10 Uniuhibited fuel blend+Ex. 5 50 21Uninhibited fuel bleud+Ex. 50 47 Uninhibited fuel blend+Ex. 25 3OUninhibited fuel blend+Ex. 8 25 27 Uninhibited fuel blend+Ex. 50 23Uninhibited fuel blend+Ex. 10 9 Uru'nhibited fuel blencH-Ex. 25 24Uninhibited fuel blend-l-Ex. 25 2 Uninllibited fuel blend+Ex. 25 3Uninhibited fuel blend+Ex. 50 9 Uninhibited fuel blend+Ex. 15. 50 2Uninhibited fuel blend+Ex. 18-.-. 10 2 Uninhibited fuel blend+Ex. 19 105 l l RUSTING The method used for te ting anti-rust properties of thefuel oils was ASTM Rust Test D-665 operated for 48 hours at 80 F. usingdistilled water. This is a dynamic test that indicates the ability toprevent rusting of ferrous metal surfaces in pipelines. tubes, etc.

Example 22 Blends of additives described in Examples 1 through 15 in thefuel oil of Example 20 were subjected to the ASTM Rust Test D665.Pertinent data are set forth in Table III.

TABLE IIL-ASTM RUST TEST D-G65 Inhibitor Concn., l Rust Test p.p.m.Result Blank fuel blend Fail.

Blank fuel hlenrH-Ex. 10 1 Pass. Blank fuel blend+Ex. 10 Do. Blank fuelblend-l-Ex. 10 l Do. Blank fuel blend+Ex. 5 Do. Blank fuel lJlend+Ex. l0Do. Blank fuel blend-l-Ex. It 1 Do. Blank fuel lilCllLll'EX. D0. Blankfuel blenrH-Ex. 10 l D0. Blank fuel Mend l-Ex Do. Blank fuel Mend-HEX.25 Do. Blank fuel l)lt'lld+EX. 25 1 Do. Blank fuel blentH-Ex. 10 1 Do.Blank fuel blend-Mix. l0 Do. Blank fuel blond-HEX. 25 1 Do. Blank fuel lleud+Ex. 5 Do.

It will be apparent, from the data set forth in Tables I through III,that the metal salts of the succinamic acids of this invention arehighly effective to reduce sedimentation and screen clogging and toinhibit rusting of ferrous metal surfaces under static and dynamicconditions. As is to be expected, results will vary among specificmaterials used. In order to accomplish any given improvement, many ofthe additives can be used in relatively small amounts, as for dynamicrust prevention. If, on the other hand, it is desired to accomplish allthe aforementioned beneficial results, this can be accomplished by useof relatively larger concentrations of the additive.

Over and above the aforesaid improvements imparted to distillate fueloil compositions by the addition agents embodied herein, such additionagents also function as inhibitors against objectionable emulsification.In that respect, the presence of the tertiary carbon atom linked to thenitrogen atom in the amide grouping of the metal salts embodied hereinis important as, for corresponding metal salts but in which the nitrogenatom is linked to a normal aliphatic group, such salts induce severeemulsification with water. In example, reference is made to Example 23showing preparation of a magnesium salt of a succinamic acid derivedfrom a normal amine (Armeen 12D) which is a mixture of primary aminescontaining 2% decylamine, 95% dodecylamine and 3% tetradecylamine. Toillustrate the importance of a tertiary carbon atom linked to thenitrogen atom in the additives embodied herein for inhibitingemulsification, fuel oil compositions were prepared by addition of themetal salt (Mg) of Example 2, the metal salt (Ba) of Example 3, and themetal salt (MG) of Example 23 in concentration of lbs/thousand barrelsof the fuel oil and the resulting compositions were subjected to theemulsion test described hereinafter.

Example 23 A mixture of 33 /3 grns. (V3 mole) of succinic anhydride,grns. (/3 mole) of Armeen 12D and 205 gms. of xylene as diluent washeated at C. for 2 hours with stirring to form the Armeen 12D succinamicacid. The Armeen 12D succinamic acid was then gradually added to 4 grns./s mole) of Mg in the form of a Mg methylate solution. The mixture wasgradually heated to 130 C. to form the Mg salt. The Mg salt, being veryviscous, was diluted with 103 gms. of isopropanol and lll 152 filteredthrough Hyflo clay. The final product, the Mg salt of Armeed 12Dsuccinamic acid, which contained 75% solvent (50% xylene+25%isopropanol), was clear and fluid at room temperature.

Anal vsis.Estimated: Mg, 0.97%; N, 1.15%. Found: Mg, 1.2%; N, 1.29%.

EMULSION T'EST The procedure for the fuel oil emulsion test is asfollows: a 200 milliliter portion of the fuel to be tested and 2Gmilliliters of distilled water are placed in a clear glass pint bottle.The bottle is tightly capped and set in an Everbach mechanical shaker ina horizontal position such that the maximum degree of agitation isafforded. The shaker is run at its maximum setting for 5 minutes. Thebottle is then removed and allowed to stand in an upright position inthe dark for 24 hours. At the end of the 24 hour settling period, theappearance of the water layer is noted. The fuel layer is siphoned off,care being taken not to disturb the oil-Water interface, and isdiscarded. A fresh portion of the fuel oil being tested is then added.The described sequence of steps is repeated. If no emulsion appears inthe water layer after this sequence has been performed ten times, theoil is considered to have passed the test. On the other hand, if, afterany 24 hour settling period in the procedure, there is any degree ofemulsification in the water layer, the fuel is considered to have failedthe test. This test procedure has been found to provide emulsions ininhibited oils similar to emulsions which occur in these same oils onlyafter prolonged periods of normal handling and storage in the field on acommercial basis.

RATING SCALE FOR REPORTING EMULSION TEST RESULTS Description 0 EmulsionRating 0 Clean break on the interface of oil and water. No dirt, skin,or bubbles present.

1 Very slight skin at the oil-water interface that usually does notbreak on tilting the bottle.

2 Skin at oil-water interface, heavier than #1 and usually accompaniedwith dirt and hubbles on the skin. No evidence of any white emulsion.

3 First sign of white emulsion. Usually forms at the bottom and in thecenter of the bottle. It is circular in shape and approximately to 1inch in diameter.

4 Approximately the same amount of emulsion on the bottom of the bottleas #3. However, emulsion is also beginning to form at oil-waterinterface and extends to downward into the water layer. Roughly 15% ofwater layer occupied by emulsion.

5 Circular emulsion at bottom of bottle extends outward and upwardresembling spokes. Emulsion at the interface a little thicker than #4.

6 viore emulsion than #5. Thin film of emulsion forming on sides ofbottle surrounding the Water layer. Water is still visible lookingthrough the sides and looking up from the bottom of the bottle.

7 Emulsion on bottom of water layer is almost solid. Emulsion on sidesof bottles is broken in a few spots enabling the operator to see thewater layer.

8 Semi-solid emulsion with perforations or bubbles similar to ahoneycomb. No water visible except that seen in the bubbles.

a few air bubbles visible.

13 11 Completely solid emulsion (Mayonnaise type).

The results obtained from the foregoing emulsion test were as follows:

Base fuel: Rating Additive:

It is apparent from the foregoing that the metal salts of thesuccinami-c acid derived from the tertiary-carbon atom amine eifectivelyinhibited emulsification (Rating 2) whereas the corresponding metal salt(Ex. 23) but prepared from the normal amine resulted in a compositionthat emulsified severely.

Although the present invention has been described with preferredembodiments, it is to be understood that modifications and variationsmay be resorted to, Without departing from the spirit and scope of thisinvention, as those skilled in the art will readily understand. Suchvariations and modifications are considered to be within the purview andscope of the appended claims.

14 What is claimed is: 1. A metal salt of the formula:

UNITED STATES PATENTS 2,604,449 7/ 1952 Bryant et a1 252-33.6 2,756,2137/1956 Dixon 25233.6 2,982,629 5/1961 Andress et a1. 44-71 3,031,2824/1962 Andress et al. 44-71 3,192,160 6/1965 Gee et al. 25233.6

TOBIAS E. LEVOW, Primary Examiner.

A. P. DEMERS, Assistant Examiner.

